Expanded anionic compounds comprising hydroxyl or quiescent reactive functionality and catalyst activators therefrom

ABSTRACT

A compound useful as a cocatalyst or cocatalyst component, especially for use as an addition polymerization catalyst compound, corresponding to the formula:  
     (A* +a ) b (Z*J* j ) −c   d ,  
     wherein:  
     A* is a cation of from 1 to 80, preferably 1 to 60 atoms, not counting hydrogen atoms, said A* having a charge +a,  
     Z* is an anion group of from 1 to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites;  
     J* independently each occurrence is a Lewis acid of from 1 to 80, preferably 1 to 60 atoms, not counting hydrogen atoms, coordinated to at least one Lewis base site of Z*, and optionally two or more such J* groups may be joined together in a moiety having multiple Lewis acidic functionality,  
     j is a number from 2 to 12 and  
     a, b, c, and d are integers from 1 to 3, with the proviso that a×b is equal to c×d, and provided further that one or more of A*, Z* or J* comprises a hydroxyl group or a polar group containing quiescent reactive functionality.

CROSS REFERENCE STATEMENT

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/219,496, filed Jul. 20, 2000.

BACKGROUND INFORMATION

[0002] The present invention relates to compounds that are useful ascatalyst components. More particularly the present invention relates tosuch compounds that are particularly adapted for use in the coordinationpolymerization of unsaturated compounds comprising an anion containingat least two Lewis basic sites which are coordinated to Lewis acids, andfurther containing a hydroxyl group or a polar group containing aquiescent reactive functionality. Such compounds are particularlyadvantageous for use in forming supported polymerization catalystswherein at least the catalyst activator is chemically attached to asubstrate material.

[0003] It is previously known in the art to activate Ziegler-Nattapolymerization catalysts, particularly such catalysts comprising Group3-10 metal complexes containing delocalized π-bonded ligand groups, bythe use of Bronsted acid salts capable of transferring a proton to forma cationic derivative or other catalytically active derivative of suchGroup 3-10 metal complex. Preferred Bronsted acid salts are suchcompounds containing a cation/anion pair that is capable of renderingthe Group 3-10 metal complex catalytically active. Suitable activatorscomprise fluorinated arylborate anions, such astetrakis(pentafluorophenyl)borate. Additional suitable anions includesterically shielded diboron anions of the formula:

[0004] wherein:

[0005] S is hydrogen, alkyl, fluoroalkyl, aryl, or fluoroaryl, Ar^(F) isfluoroaryl, and X¹ is either hydrogen or halide, disclosed in U.S. Pat.No. 5,447,895. Additional examples include carborane compounds such asare disclosed and claimed in U.S. Pat. No. 5,407,884.

[0006] Examples of preferred charge separated (cation/ anion pair)activators are ammonium, sulfonium, or phosphonium salts capable oftransferring a hydrogen ion, disclosed in U.S. Pat. No. 5,198,401, U.S.Pat. No. 5,132,380, U.S. Pat. No. 5,470,927 and U.S. Pat. No. 5,153,157,as well as oxidizing salts such as ferrocenium, silver or lead salts,disclosed in U.S. Pat. No. 5,189,192 and U.S. Pat. No. 5,321,106 andstrongly Lewis acidic salts such as carbonium or silylium salts,disclosed in U.S. Pat. No. 5,350,723 and U.S. Pat. No. 5,625,087.

[0007] Further suitable activators for the above metal complexes includestrong Lewis acids including tris(perfluorophenyl)borane andtris(perfluorobiphenyl)borane. The former composition has beenpreviously disclosed for the above stated end use in EP-A-520,732,whereas the latter composition is similarly disclosed by Marks, et al.,in J. Am. Chem. Soc., 118, 12451-12452 (1996).

[0008] Despite the satisfactory performance of the foregoing catalystactivators under a variety of polymerization conditions, there is stilla need for improved cocatalysts for use in the activation of variousmetal complexes especially under a variety of reaction conditions.Accordingly, it would be desirable if there were provided compounds thatcould be employed in solution, slurry, gas phase or high pressurepolymerizations and under homogeneous or heterogeneous processconditions having improved activation properties. In particular, itwould be desirable to provide compounds that may be chemically bonded tosupport materials to prepare supported catalyst components havingimproved resistance to solvent removal and loss from the particlesurface.

SUMMARY OF THE INVENTION

[0009] According to the present invention there are now providedcompounds useful as catalyst activators corresponding to the formula:

(A*^(+a))_(b)(Z*J*_(j))^(−c) _(d),

[0010] wherein:

[0011] A* is a cation of from 1 to 80, preferably 1 to 60 atoms, notcounting hydrogen atoms, said A* having a charge +a,

[0012] Z* is an anion group of from 1 to 50, preferably 1 to 30 atoms,not counting hydrogen atoms, further containing two or more Lewis basesites;

[0013] J* independently each occurrence is a Lewis acid of from 1 to 80,preferably 1 to 60 atoms, not counting hydrogen atoms, coordinated to atleast one Lewis base site of Z*, and optionally two or more such J*groups may be joined together in a moiety having multiple Lewis acidicfunctionality,

[0014] j is a number from 2 to 12 and

[0015] a, b, c, and d are integers from 1 to 3, with the proviso thata×b is equal to c×d, and provided further that one or more of A*, Z* orJ* comprises a hydroxyl group or a polar group containing quiescentreactive functionality.

[0016] The foregoing compounds, in particular, those containingquiescent reactive functionality may be utilized in combination with oneor more Group 3-10 or Lanthanide metal complexes to form catalystcompositions for polymerization of addition polymerizable monomers,especially ethylenically unsaturated monomers, most preferably,C_(2-20,000) α-olefins. Additionally, the compounds may be utilized toform latent activators, that is, compounds that may themselves not causea metal complex to become catalytically active, but which may beconverted to such a compound, by, for example, in-situ reaction of thehydroxyl group or quiescent reactive functionality or its derivativewith a Lewis acid, especially an aluminum hydrocarbyl compound, or analkali metal halide or ammonium halide salt. Moreover, the compounds maybe deposited onto solid supports, such as by impregnation, surfacedeposition, physisorption or chemical reaction with the support,reactive functionality of the support, or chemical modifiers associatedwith the support, to form heterogeneous catalyst components for use inpreparing heterogeneous catalyst compositions for use in polymerizationof the foregoing monomers.

[0017] In one embodiment of the invention, the foregoing compounds areused to form supported catalyst components by reaction of the hydroxylgroup thereof with reactive functionality of a support material, or byconversion of the quiescent reactive functionality to a reactivefunctionality and reaction thereof with reactive functionality of asupport material. The resulting supported catalyst components are highlyresistant to loss of activator compound in a liquid reaction medium suchas occurs in a slurry polymerization. One or more Group 3-10 orLanthanide metal complexes, preferably a Group 4 metal complex, andadditional additives, modifiers and adjuvants may be added to thecatalyst component, either before, after or simultaneous with additionof the cocatalyst of the present invention, to form the fully formulatedcatalyst composition.

[0018] Additionally according to the present invention there is provideda catalyst composition for polymerization of an ethylenicallyunsaturated, polymerizable monomer comprising, in combination, the abovedescribed activated derivative compound, a Group 3-10 metal complex thatis capable of activation to form an addition polymerization catalyst, orthe reaction product of such combination, and optionally a support.

[0019] Additionally according to the present invention there is provideda process for polymerization of one or more ethylenically unsaturated,polymerizable monomers comprising contacting the same, optionally in thepresence of an inert aliphatic, alicyclic or aromatic hydrocarbon, withthe above catalyst composition or supported catalyst composition.

[0020] The foregoing compounds are uniquely adapted for use inactivation of a variety of metal complexes, especially Group 4 metalcomplexes, under standard and atypical olefin polymerization conditions.Because of this fact, the foregoing compounds are capable of forminghighly desirable olefin polymers in high efficiency.

DETAILED DESCRIPTION OF THE INVENTION

[0021] All references herein to elements belonging to a certain Grouprefer to the Periodic Table of the Elements published and copyrighted byCRC Press, Inc., 1995. Also any reference to the Group or Groups shallbe to the Group or Groups as reflected in this Periodic Table of theElements using the IUPAC system for numbering groups. When referred toherein, the teachings of any patent, patent application or publicationare hereby incorporated by reference herein.

[0022] The catalyst activators of the invention are furthercharacterized in the following manner. A*^(+a) is desirably chosen toprovide overall neutrality to the compound and to not interfere withsubsequent catalytic activity. Moreover, the cation may participate inthe formation of the active catalyst species, desirably through a protontransfer, oxidation, or ligand abstraction mechanism, or a combinationthereof. Additionally, certain cations beneficially improve thesolubility of the resulting activator in particular reaction media underuse conditions. For example, in the homopolymerization orcopolymerization of aliphatic olefins, particularly in the solutionphase, an aliphatic diluent is commonly used. Accordingly, cationicspecies that are relatively soluble in such reaction media, or renderthe catalyst activator more soluble therein are highly preferred.

[0023] Examples of suitable cations include ammonium, sulfonium,phosphonium, oxonium, carbonium, and silylium cations, preferably thosecontaining up to 80 atoms not counting hydrogen, as well as ferrocenium,Ag⁺, Pb⁺², or similar oxidizing cations. As previously mentioned, thecation may also comprise a hydroxyl group or a polar group containingquiescent reactive functionality. In a preferred embodiment, a, b, c andd are all equal to one.

[0024] Z* can be any anionic moiety containing two or more Lewis basicsites. Preferably, the Lewis base sites are on different atoms of apolyatomic anionic moiety. Desirably, such Lewis basic sites arerelatively sterically accessible to the Lewis acid, J*. Preferably theLewis basic sites are on nitrogen or carbon atoms. Examples of suitableZ* anions include cyanide, azide, amide and substituted amide, amidinideand substituted amidinide, dicyanamide, imidazolide, substitutedimidazolide, imidazolinide, substituted imidazolinide, tricyanomethide,tetracycanoborate, puride, squarate, 1,2,3-triazolide, substituted1,2,3-triazolide, 1,2,4-triazolide, substituted 1,2,4-triazolide,pyrimidinide, substituted pyrimidinide, tetraimidazoylborate andsubstituted tetraimidazoylborate anions, wherein each group, if present,is a halo-, hydrocarbyl-, halohydrocarbyl-, silyl-, (including mono-,di- and tri(hydrocarbyl)silyl-), silylhydrocarbyl-, halocarbyl- orhydroxyl-group, or a polar group containing quiescent reactivefunctionality, or two such groups together form a saturated orunsaturated ring- or multiple ring-system.

[0025] Preferred Z* groups are: imidazolide, 2-nonadecylimidazolide,2-undecylimidazolide, 2-tridecylimidazolide, 2-pentadecylimidazolide,2-heptadecylimidazolide, 2-nonadecylimidazolide,4,5-difluoroimidazolide, 4,5-dichloroimidazolide,4,5-dibromoimidazolide, 4,5-bis(heptadecyl)imidazolide,4,5-bis(undecyl)imidazolide, imidazolinide, 2-nonadecylimidazolinide,2-undecylimidazolinide, 2-tridecylimidazolinide,2-pentadecylimidazolinide, 2-heptadecylimidazolinide,2-nonadecylimidazolinide, 4,5-difluoroimidazolinide,4,5-dichloroimidazolinide, 4,5-dibromoimidazolinide,4,5-bis(heptadecyl)imidazolinide, 4,5-bis(undecyl)imidazolinide,didecylamide, piperidinide, 4,4-dimethylimidazolinide,tetra-5-pyrimidinylborate, pyrimidinide, 5,6-dichlorobenzimidazolide,4,5-dicyanoimidazolide, and 5,6-dimethylbenzimidazolide anions, or saidZ* groups that are further substituted with a hydroxyl group or a polargroup containing quiescent reactive functionality.

[0026] Coordinated to the Lewis base sites of the anion are from 2 to 12Lewis acids, J*, two or more of which may be joined together in a moietyhaving multiple Lewis acidic functionality. Optionally, said J* groupmay comprise a hydroxyl group or a polar group containing quiescentreactive functionality, so long as such functionality does not interferewith the Lewis acid functionality of the group. Preferably, from 2 to 4J* groups having from 3 to 100 atoms not counting hydrogen are present.

[0027] More specific examples of the foregoing Lewis acid compounds, J*,correspond to the formula:

[0028] wherein:

[0029] M* is aluminum, gallium or boron;

[0030] R¹ and R² independently each occurrence are hydride, halide, or ahydrocarbyl, halocarbyl, halohydrocarbyl, dialkylamido, alkoxide, oraryloxide group of up to 20 carbons, optionally substituted with ahydroxyl group or a polar group containing quiescent reactivefunctionality, and

[0031] Ar^(f1)-Ar^(f2) in combination, independently each occurrence, isa divalent fluoro-substituted aromatic group of from 6 to 20 carbons,optionally substituted with a hydroxyl group or a polar group containingquiescent reactive functionality.

[0032] Highly preferred Lewis acids are aluminum or boron compoundscorresponding to the formula: AlR¹ ₃, or BR¹ ₃, wherein R¹ independentlyeach occurrence is selected from hydrocarbyl, halocarbyl, andhalohydrocarbyl radicals, or such groups further substituted with ahydroxyl group or a polar group containing quiescent reactivefunctionality, said R¹ having up to 20 carbons. In a more highlypreferred embodiment, R¹ is a fluorinated C₁₋₂₀ hydrocarbyl group, mostpreferably, a fluorinated aryl group, especially, pentafluorophenyl.

[0033] Preferred examples of the foregoing Lewis acid groups containingmultiple Lewis acid sites are:

[0034] By the term “polar group containing quiescent reactivefunctionality” is meant an oxygen, nitrogen, sulfur, or phosphoruscontaining ligand group that is capped or protected and thereby renderedrelatively inert to reaction conditions used in the synthesis or use ofthe present compounds, but wherein the capping or protecting groups maybe later removed, if desired, thereby generating a reactive polarfunctional group, especially a hydroxyl group or metallated derivativethereof. Suitable reactive polar functional groups include hydroxyl,thiol, amine, and phosphine groups, or hydrocarbyl-, alkali metal- orBronsted acid salt-derivatives thereof. Suitable quiescent reactivefunctionality includes the trihydrocarbyllsilyl-, trihydrocarbylgermyl-,dihydrocarbylaluminum-, hydrocarbylzinc- orhydrocarbylmagnesium-functionalized derivative of the foregoing polargroups. Particularly preferred polar containing quiescent reactivefunctional groups are trihydrocarbylsiloxy,trihydrocarbylsiloxy-substituted hydrocarbyl, dihydrocarbylaluminoxy anddihydrocarbylaluminoxy substituted hydrocarbyl groups. Especiallypreferred are the trialkylsiloxy- or dialkylaluminoxy-derivatives ofsuch polar functional groups, containing from 1 to 6 carbon in eachalkyl group. Especially preferred quiescent reactive functional groupsare trimethylsiloxy-groups and diethylaluminoxy-groups.

[0035] Such polar group containing quiescent reactive functionality isactivated by reaction with a metal hydrocarbyl-, metal halocarbyl-,hydrocarbylmetaloxy- or metal halohydrodarbyl-compound under ligandexchange conditions, thereby producing a neutral hydrocarbon,halohydrocarbon, trimethylsilylhydrocarbon,trimethylsilylhalohydrocarbon or trimethylsilylhalocarbon compound as aby-product. The hydroxyl group or polar group containing quiescentreactive functionality may also be employed to react with hydroxyl-,alkylmetal-, hydrocarbylsilyl-, or hydrocarbylsiloxy-functionality of asolid, particulated, support material, optionally after conversion to ametallated or protonated intermediate. This results in tethering orchemically attaching the activator to the surface of the solid,particulated, support material. The resulting substance demonstratesenhanced resistance to loss or removal when exposed to liquids in apolymerization process.

[0036] In a preferred embodiment, the foregoing hydroxyl group or polargroup containing quiescent reactive functionality is located in the Z*ligand. Examples include hydroxyl, trialkylsiloxy-,trialkylsiloxyalkyl-, trialkylsiloxyaryl-, anddialkylaluminoxyaryl-substituted derivatives of imidazolide,2-(C₁₋₃₀hydrocarbyl)imidazolide, 4,5-dihaloimidazolide,4,5-di(C₁₋₃₀hydrocarbyl)imidazolide, 4,5-benzylimidazolide,2-(C₁₋₃₀hydrocarbyl)-4,5-benzimidazolide, 1,3,4-triazolide,2-(C₁₋₃₀hydrocarbyl-1,3,4-triazolide, 1,2,3-triazolide,4,5-benz-1,2,3-triazolide, imidazolinide,2-(C₁₋₃₀hydrocarbyl)imidazolinide, 4,5-dihaloimidazolinide, and5,6-dimethylbenzimidazolide. Especially preferred examples includehydroxyaryl, trimethylsiloxyaryl-, and dialkylaluminoxyaryl-substitutedderivatives of imidazolide, 2-(C₁₋₃₀alkyl)imidazolide,4,5-di(C₁₋₃₀alkyl)imidazolide, 4,5-benzimidazolide, 1,3,4-triazolide,2-(C₁₋₃₀alkyl-1,3,4-triazolide, and 1,2,3-triazolide.

[0037] Especially suitable expanded anion compounds according to thepresent invention include the ammonium, phosphonium, sulfonium, oxonium,carbonium, silylium, lead (II), silver or ferrocenium salts ofhydroxylphenyl-, trimethylsiloxyphenyl-, anddialkylaluminoxyphenyl-substituted derivatives of:bis(tris(pentafluorophenyl)borane)imidazolide,bis(tris(pentafluorophenyl)borane)-2-undecyl-imidazolide,bis(tris(pentafluorophenyl)borane)imidazolinide,bis(tris(pentafluorophenyl)-borane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-benzimidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)borane)1,3,4-triazolide,bis(tris(pentafluorophenyl)borane)-2-undecyl-1,3,4-triazolide,bis(tris(pentafluorophenyl)alumane)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)alumane)imidazolinide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,bis(tris-(pentafluorophenyl)alumane)-4,5-benzimidazolide,bis(tris(pentafluoro-phenyl)alumane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-1,3,4-triazolide, andbis(tris(pentafluorophenyl)alumane)-2-undecyl-1,3,4-triazolide.

[0038] Preferred expanded anion compounds are the ammonium salts of theforegoing derivatives, especially those which comprisetrihydrocarbyl-substituted ammonium cations, especiallytrimethylammonium-, triethylammonium-, tripropylammonium-,tri(n-butyl)ammonium-, methyldi(octadecyl)ammonium-,methyldi(tetradecyl)ammonium-, methyl(tetradecyl) (octadecyl)ammonium-,N,N-dimethylanilinium-, N,N-diethylanilinium-,N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-,N,N-di(tetradecyl)-2,4,6-trimethylanilinium)-,N,N-di(octadecyl)lanilinium-,N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, andmethyidicyclohexylammonium-cations, or mixtures thereof.

[0039] Most preferred ammonium cation containing salts are thosecontaining trihydrocarbyl-substituted ammonium cations containing one ortwo C₁₀-C₄₀ alkyl groups, especially methylbis(octadecyl)ammonium- andmethylbis(tetradecyl)ammonium-cations. It is further understood that thecation may comprise a mixture of hydrocarbyl groups of differinglengths. For example, the protonated ammonium cation derived from thecommercially available long chain amine comprising a mixture of two C₁₄,C₁₆ or C₁₈ alkyl groups and one methyl group. Such amines are availablefrom Witco Corp., under the trade name Kemamine™ T9701, and fromAkzo-Nobel under the trade name Armeen™ M2HT.

[0040] The foregoing cocatalysts (illustrated by those havingsubstituted-imidazolide, imidazolinide, benzimidazolide,1,3,4-triazolide, 1,2,3-triazolide, or 4,5-benzyl-1,2,3-triazolideanions containing one or more hydroxyl-, trimethylsiloxy-,trimethylsiloxyalkyl-, or trimethylsiloxyaryl-groups) may be depictedschematically as follows:

[0041] wherein:

[0042] A*⁺ is a monovalent cation as previously defined, and preferablyis a trihydrocarbyl ammonium cation, containing one or two C₁₀₋₄₀ alkylgroups, especially the methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-cation,

[0043] R⁴, independently each occurrence, is hydrogen or ahydroxyhydrocarbyl, halo, hydrocarbyl, halocarbyl, halohydrocarbyl,silylhydrocarbyl, or silyl group, (including mono-, di- andtri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen,preferably C₁₋₂₀ alkyl group, or a quiescent reactive group, with theproviso that at least one R⁴ group contains a hydroxyhydrocarbyl groupor a quiescent reactive group, preferably a hydroxyaryl,trialkylsiloxy-, trialkylsiloxyalkyl-, trialkylsiloxyaryl-, ordialkyllaluminoxyaryl-ligand, more preferably a trimethylsiloxy-,trimethylsiloxymethyl-, trimethylsiloxyphenyl-, ordiethylaluminoxyphenyl-ligand, and

[0044] J*′ is tris(pentafluorophenyl)borane ortris(pentafluorophenyl)alumane).

[0045] Examples of the most highly preferred catalyst activators hereininclude the forgoing trihydrocarbylammonium-, especially,methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium-salts of:

[0046]bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)imidazolide,

[0047]bis(tris(pentafluorophenyl)borane)-2-(p-hydroxybiphenyl)imidazolide,

[0048]bis(tris(pentafluorophenyl)borane)-5-(p-hydroxynaphthyl)imidazolide,

[0049]bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-hydroxyphenyl)imidazolide,

[0050]bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-hydroxyphenyl)imidazolide,

[0051]bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-bis(undecyl)imidazolide,

[0052]bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-bis(heptadecyl)imidazolide,

[0053]bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)imidazolinide,

[0054]bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-1,3,4-triazolide,

[0055]bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-benziimidazolide;

[0056]bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)imidazolide,

[0057]bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-trimethylsiloxyphenyl)imidazolide,

[0058]bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-trimethylsiloxyphenyl)imidazolide,

[0059]bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(undecyl)imidazolide,

[0060]bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(heptadecyl)imidazolide,

[0061]bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)imidazolinide,

[0062]bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-1,3,4-triazolide,

[0063]bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-benziimidazolide;

[0064]bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imidazolide,

[0065]bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxybiphenyl)imidazolide,

[0066]bis(tris(pentafluorophenyl)borane)-5-(p-diethylaluminoxynaphthyl)imidazolide,

[0067]bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-diethylaluminoxyphenyl)imidazolide,

[0068]bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-diethylaluminoxyphenyl)imidazolide,

[0069]bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(undecyl)imidazolide,

[0070]bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(heptadecyl)imidazolide,

[0071]bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imidazolinide,

[0072]bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-1,3,4-triazolide,

[0073]bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-benziimidazolide;

[0074]bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)imidazolide,

[0075]bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-hydroxyphenyl)imidazolide,

[0076]bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-hydroxyphenyl)imidazolide,

[0077]bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-bis(undecyl)imidazolide,

[0078]bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-bis(heptadecyl)imidazolide,

[0079]bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)imidazolinide,

[0080]bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-1,3,4-triazolide,

[0081]bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-benziimidazolide;

[0082]bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)imidazolide,

[0083]bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-trimethylsiloxyphenyl)imidazolide,

[0084]bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-trimethylsiloxyphenyl)imidazolide,

[0085]bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(undecyl)imidazolide,

[0086]bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(heptadecyl)imidazolide,

[0087]bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)imidazolinide,

[0088]bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-1,3,4-triazolide,

[0089]bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-benziimidazolide,

[0090]bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)imidazolide,

[0091]bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-diethylaluminoxyphenyl)imidazolide,

[0092]bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-diethylaluminoxyphenyl)imidazolide,

[0093]bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(undecyl)imidazolide,

[0094]bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(heptadecyl)imidazolide,

[0095]bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)imidazolinide,

[0096]bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-1,3,4-triazolide,and

[0097]bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-benziimidazolide.

[0098] The compounds may be prepared by a condensation reaction betweenthe alkali metal salt of the anion, Z*, and a Lewis acid, J*, preferablyunder phase transfer conditions, using for example a crown ether tosolubilize the alkali metal salt if necessary, followed by a metathesisreaction with the corresponding halide salt of the cation, A*^(+a).Certain of the cocatalysts are also amenable to preparation via a onestep, single reactor process. For example, the ammonium- orphosphonium-substituted hydroxyl group or quiescent reactivegroup-substituted imidiazolide salts can be prepared by contacting theLewis acid, J*, or its Lewis base adduct, such as an etherate, with theneutral compound corresponding to the anion, Z*. Both reactants aredesirably relatively lipophilic, such that the reaction can be performedin non-polar solvents. Addition of the free base corresponding to thecation, A*^(+a), results in formation of the charge separated species,which may be recovered from the reaction mixture by devolatilization orused without further purification.

[0099] The corresponding reactive hydroxyl-, thiol, amine, or phosphinecontaining compound (or its metal or ammonium salt derivative) may begenerated or produced in situ by reaction of the quiescent reactivegroups of the present compounds with any suitable reactant, such as ahydrocarbon, a metal fluoride, an ammonium fluoride, or an acid, therebyremoving the capping or protecting group(s).

[0100] Due to the presence of the hydroxyl group or quiescent reactivefunctionality in the compounds of the present invention, or reactivederivatives thereof, the present compounds may be readily attached to areactive substrate, such as a particulated solid containing reactivehydrocarbyl groups, especially hydrocarbylmetal- orhydrocarbylmetalloid-functionality. Examples include alumina, silica,aluminosilicates, and aluminum magnesium silicate materials, containingreactive hydroxyl- or hydrocarbyl-functionality, and such materialstreated with any substance to impart reactive metal-hydrocarbyl ormetalloid-hydrocarbyl functionality. Examples of such treatingsubstances include trihydrocarbyl aluminum compounds, chlorosilanecompounds, and mono- or di-hydrocarbylsilane compounds that react with aportion or all of reactive surface hydroxyl functionality of thesubstrate to form a “capped” derivative. This technique is known in theart and disclosed for example in U.S. Pat. No. 6,087,293.

[0101] Suitable catalysts for use in combination with the foregoingcocatalysts include any compound or complex of a metal of Groups 3-10 ofthe Periodic Table of the Elements capable of being activated topolymerize ethylenically unsaturated compounds by the presentactivators. Examples include Group 10 diimine derivatives correspondingto the formula:

[0102] wherein

[0103] M* is Ni(II) or Pd(II);

[0104] K is halo, hydrocarbyl, or hydrocarbyloxy;

[0105] and the two nitrogen atoms are linked by a bridging system.

[0106] Such catalysts have been previously disclosed in J. Am. Chem.Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), andOrganometallics, 16, 1514-1516, (1997).

[0107] Additional catalysts include derivatives of Group 3, 4, orLanthanide metals which are in the +2, +3, or +4 formal oxidation state.Preferred compounds include metal complexes containing from 1 to 3π-bonded anionic or neutral ligand groups, which may be cyclic ornon-cyclic delocalized π-bonded anionic ligand groups. Exemplary of suchπ-bonded anionic ligand groups are conjugated or nonconjugated, cyclicor non-cyclic dienyl groups, allyl groups, boratabenzene groups,phosphole, and arene groups. By the term “π-bonded” is meant that theligand group is bonded to the transition metal by a sharing of electronsfrom a partially delocalized π-bond.

[0108] Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedmetalloid radicals wherein the metalloid is selected from Group 14 ofthe Periodic Table of the Elements, and such hydrocarbyl- orhydrocarbyl-substituted metalloid radicals further substituted with aGroup 15 or 16 hetero atom containing moiety. Included within the term“hydrocarbyl” are C₁₋₂₀ straight, branched and cyclic alkyl radicals,C₆₋₂₀ aromatic radicals, C₇₋₂₀ alkyl-substituted aromatic radicals, andC₇₋₂₀ aryl-substituted alkyl radicals. In addition two or more suchradicals may together form a fused ring system, including partially orfully hydrogenated fused ring systems, or they may form a metallocyclewith the metal. Suitable hydrocarbyl-substituted organometalloidradicals include mono-, di- and tri-substituted organometalloid radicalsof Group 14 elements wherein each of the hydrocarbyl groups containsfrom 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substitutedorganometalloid radicals include trimethylsilyl, triethylsilyl,ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, andtrimethylgermyl groups. Examples of Group 15 or 16 hetero atomcontaining moieties include amine, phosphine, ether or thioethermoieties or divalent derivatives thereof, e.g. amide, phosphide, etheror thioether groups bonded to the transition metal or Lanthanide metal,and bonded to the hydrocarbyl group or to the hydrocarbyl-substitutedmetalloid containing group.

[0109] Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzene groups, as well as hydrocarbyl-silyl-(including mono-, di-, or tri(hydrocarbyl)silyl) substituted derivativesthereof. Preferred anionic, delocalized π-bonded groups arecyclopentadienyl, pentamethylcyclopentadienyl,tetramethylcyclopentadienyl,tetramethyl(trimethylsilyl)-cyclopentadienyl, indenyl,2,3-dimethylindenyl, fluorenyl, 2-methylindenyl,2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, andtetrahydroindenyl.

[0110] The boratabenzenes are anionic ligands that are boron containinganalogues to benzene. They are previously known in the art having beendescribed by G. Herberich, et al., in Organometallics, 14,1, 471-480(1995). Preferred boratabenzenes correspond to the formula:

[0111] wherein R″ is selected from the group consisting of hydrocarbyl,silyl, N,N-dihydrocarbylamino, or germyl, said R″ having up to 20non-hydrogen atoms. In complexes involving divalent derivatives of suchdelocalized π-bonded groups one atom thereof is bonded by means of acovalent bond or a covalently bonded divalent group to another atom ofthe complex thereby forming a bridged system.

[0112] Phospholes are anionic ligands that are phosphorus containinganalogues to a cyclopentadienyl group. They are previously known in theart having been described by WO 98/50392, and elsewhere. Preferredphosphole ligands correspond to the formula:

[0113] wherein R″ is selected from the group consisting of hydrocarbyl,silyl, N,N-dihydrocarbylamino, or germyl, said R″ having up to 20non-hydrogen atoms, and optionally one or more R″ groups may be bondedtogether forming a multicyclic fused ring system, or form a bridginggroup connected to the metal. In complexes involving divalentderivatives of such delocalized π-bonded groups one atom thereof isbonded by means of a covalent bond or a covalently bonded divalent groupto another atom of the complex thereby forming a bridged system.

[0114] Phosphinimine/cyclopentadienyl complexes are disclosed inEP-A-890581 and correspond to the formula[(R***)₃—P=N]_(b)M**(Cp)(L¹)_(3-b), wherein:

[0115] R*** is a monovalent ligand, illustrated by hydrogen, halogen, orhydrocarbyl, or two R*** groups together form a divalent ligand,

[0116] M** is a Group 4 metal,

[0117] Cp is cyclopentadienyl, or similar delocalized π-bonded group,

[0118] L¹ is a monovalent ligand group, illustrated by hydrogen, halogenor hydrocarbyl,

[0119] b is a number from 1 to 3; and

[0120] n is 1 or 2.

[0121] A suitable class of catalysts are transition metal complexescorresponding to the formula:

L_(pl)MX_(m)X′_(n)X″_(p), or a dimer thereof

[0122] wherein:

[0123] Lp is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 non-hydrogen atoms, optionally two Lp groups may bejoined together forming a bridged structure, and further optionally oneLp may be bound to X;

[0124] M is a metal of Group 4 of the Periodic Table of the Elements inthe +2, +3 or +4 formal oxidation state;

[0125] X is an optional, divalent group of up to 50 non-hydrogen atomsthat together with Lp forms a metallocycle with M;

[0126] X′ is an optional neutral ligand having up to 20 non-hydrogenatoms;

[0127] X″ each occurrence is a monovalent, anionic moiety having up to40 non-hydrogen atoms, optionally, two X″ groups may be covalently boundtogether forming a divalent dianionic moiety having both valences boundto M, or, optionally 2 X″ groups may be covalently bound together toform a neutral, conjugated or nonconjugated diene that is π-bonded to M(whereupon M is in the +2 oxidation state), or further optionally one ormore X″ and one or more X′ groups may be bonded together thereby forminga moiety that is both covalently bound to M and coordinated thereto bymeans of Lewis base functionality;

[0128] l is 0, 1 or 2;

[0129] m is 0 or 1;

[0130] n is a number from 0 to 3;

[0131] p is an integer from 0 to 3; and

[0132] the sum, l+m+p, is equal to the formal oxidation state of M,except when 2 X″ groups together form a neutral conjugated ornon-conjugated diene that is π-bonded to M, in which case the sum l+m isequal to the formal oxidation state of M.

[0133] Preferred complexes include those containing either one or two Lpgroups. The latter complexes include those containing a bridging grouplinking the two Lp groups. Preferred bridging groups are thosecorresponding to the formula (ER*₂)_(X), B(NR**₂), or B(NR**₂)₂, whereinE is silicon, germanium, tin, or carbon, R* independently eachoccurrence is hydrogen or a group selected from silyl, hydrocarbyl,hydrocarbyloxy, and combinations thereof, said R* having up to 30 carbonor silicon atoms, R** independently each occurrence is a group selectedfrom silyl, hydrocarbyl, and combinations thereof, said R** having up to30 carbon or silicon atoms, and x is 1 to 8. Preferably, R*independently each occurrence is methyl, ethyl, propyl, benzyl, butyl,phenyl, methoxy, ethoxy, or phenoxy, and R** is methyl, ethyl, propyl,benzyl or butyl.

[0134] Examples of the complexes containing two Lp groups are compoundscorresponding to the formula:

[0135] wherein:

[0136] M is titanium, zirconium or hafnium, preferably zirconium orhafnium, in the +2 or +4 formal oxidation state;

[0137] R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system, and

[0138] X″ independently each occurrence is an anionic ligand group of upto 40 non-hydrogen atoms, or two X″ groups together form a divalentanionic ligand group of up to 40 non-hydrogen atoms or together are aconjugated diene having from 4 to 30 non-hydrogen atoms forming aπ-complex with M, whereupon M is in the +2 formal oxidation state, and

[0139] R*, R**, E and x are as previously defined, preferably (ER*₂)x isdimethylsilandiyl or ethylene, and BNR**₂ isdi(isopropyl)aminoborandiyl.

[0140] The foregoing metal complexes are especially suited for thepreparation of polymers having stereoregular molecular structure. Insuch capacity it is preferred that the complex possesses C_(s) symmetryor possesses a chiral, stereorigid structure. Examples of the first typeare compounds possessing different delocalized π-bonded systems, such asone cyclopentadienyl group and one fluorenyl group. Similar systemsbased on Ti(IV) or Zr(IV) were disclosed for preparation of syndiotacticolefin polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256(1980). Examples of chiral structures include rac bis-indenyl complexes.Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparationof isotactic olefin polymers in Wild et al., J. Organomet. Chem., 232,233-47, (1982).

[0141] Exemplary bridged ligands containing two π-bonded groups are:dimethylbis(cyclopentadienyl)silane,dimethylbis(tetramethylcyclopentadienyl)silane,dimethylbis(2-ethylcyclopentadien-1-yl)silane,dimethylbis(2-t-butylcyclopentadien-1-yl)silane,2,2-bis(tetramethylcyclopentadienyl)propane,dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane,dimethylbis(fluoren-1-yl)silane,dimethylbis(tetrahydrofluoren-1-yl)silane,dimethylbis(2-methyl-4-phenylinden-1-yl)silane,dimethylbis(2-methylinden-1-yl)silane,di(isopropyl)aminobis(cyclopentadien-1-yl)borandiyl,di(isopropyl)aminobis(2-methyl-4-phenylinden-1-yl)-borandiyl,di(isopropyl)aminobis(2-methylinden-1-yl)borandiyl,dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane,(1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane,(1,2-bis(cyclopentadienyl)ethane, anddimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

[0142] Preferred X″ groups are selected from hydride, hydrocarbyl,silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

[0143] Complexes containing two Lp groups including bridged complexessuitable for use in the present invention include:

[0144] bis(cyclopentadienyl)zirconiumdimethyl,

[0145] bis(cyclopentadienyl)zirconium dibenzyl,

[0146] bis(cyclopentadienyl)zirconium methyl benzyl,

[0147] bis(cyclopentadienyl)zirconium methyl phenyl,

[0148] bis(cyclopentadienyl)zirconiumdiphenyl,

[0149] bis(cyclopentadienyl)titanium-allyl,

[0150] bis(cyclopentadienyl)zirconiummethylmethoxide,

[0151] bis(cyclopentadienyl)zirconiummethylchloride,

[0152] bis(pentamethylcyclopentadienyl)zirconiumdimethyl,

[0153] bis(pentamethylcyclopentadienyl)titaniumdimethyl,

[0154] bis(indenyl)zirconiumdimethyl,

[0155] indenylfluorenylzirconiumdimethyl,

[0156] bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),

[0157] bis(indenyl)zirconiummethyltrimethylsilyl,

[0158] bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl,

[0159] bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,

[0160] bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,

[0161] bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,

[0162] bis(pentamethylcyclopentadienyl)zirconiummethylchloride,

[0163] bis(methylethylcyclopentadienyl)zirconiumdimethyl,

[0164] bis(butylcyclopentadienyl)zirconiumdibenzyl,

[0165] bis(t-butylcyclopentadienyl)zirconiumdimethyl,

[0166] bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,

[0167] bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,

[0168] bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,

[0169] dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl,

[0170] dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium (III)allyl

[0171] dimethylsilyl-bis(t-butylcyclopentadienyl)zirconiumdibenzyl,

[0172] dimethylsilyl-bis(n-butylcyclopentadienyl)zirconiumbis(trimethylsilyl),

[0173] (methylene-bis(tetramethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

[0174] (methylene-bis(n-butylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

[0175] dimethylsilyl-bis(indenyl)zirconiumbenzylchloride,

[0176] dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl,

[0177] dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

[0178]dimethylsilyl-bis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,

[0179] dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,dimethylsilyl-bis(tetrahydroindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

[0180] di(isopropylamino)borandiylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

[0181] dimethylsilyl-bis(tetrahydrofluorenyl)zirconiumbis(trimethylsilyl),

[0182] (isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl,and

[0183] dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconiumdimethyl.

[0184] A further class of metal complexes utilized in the presentinvention corresponds to the preceding formula Lp_(l)MX_(m)X′_(n)X∝_(p),or a dimer thereof, wherein X is a divalent group of up to 50non-hydrogen atoms that together with Lp forms a metallocycle with M.

[0185] Preferred divalent X groups include groups containing up to 30non-hydrogen atoms comprising at least one atom that is oxygen, sulfur,boron or a member of Group 14 of the Periodic Table of the Elementsdirectly attached to the delocalized =-bonded group, and a differentatom, selected from the group consisting of nitrogen, phosphorus, oxygenor sulfur that is covalently bonded to M.

[0186] A preferred class of such Group 4 metal coordination complexesused according to the present invention corresponds to the formula:

[0187] wherein:

[0188] M is titanium or zirconium, preferably titanium in the +2, +3, or+4 formal oxidation state;

[0189] R¹ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

[0190] each X″ is a halo, hydrocarbyl, hydrocarbyloxy or silyl group,said group having up to 20 non-hydrogen atoms, or two X″ groups togetherform a neutral C₅₋₃₀ conjugated diene or a divalent derivative thereof;

[0191] Y is —O—, —S—, —NR*—, —PR*—; and

[0192] Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂,GeR*₂, or B(NR**₂) wherein R* and R** are as previously defined.

[0193] Illustrative Group 4 metal complexes of the latter formula thatmay be employed in the practice of the present invention include:

[0194] cyclopentadienyltitaniumtrimethyl,

[0195] indenyltitaniumtrimethyl,

[0196] octahydrofluorenyltitaniumtrimethyl,

[0197] tetrahydroindenyltitaniumtrimethyl,

[0198] tetrahydrofluorenyltitaniumtrimethyl,

[0199](tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

[0200](tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

[0201](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumdibenzyl,

[0202](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumdimethyl,

[0203](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdimethyl,

[0204] (tert-butylamido)(tetramethyl-η⁵-indenyl)dimethylsilanetitaniumdimethyl,

[0205] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) 2-(dimethylamino)benzyl;

[0206](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) allyl,

[0207](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) 2,4-dimethylpentadienyl,

[0208](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0209](tert-butylamido)(tetramethl-η⁵-cylopentadienyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0210] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (ii)1,4-diphenyl-1,3-butadiene,

[0211] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)2,4-hexadiene,

[0212] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)2,3-dimethyl-1,3-butadiene,

[0213] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)isoprene,

[0214] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

[0215] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)2,3-dimethyl-1,3-butadiene,

[0216] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)isoprene

[0217] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)dimethyl

[0218] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)dibenzyl

[0219] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

[0220] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II), 1,3-pentadiene,

[0221] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

[0222] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

[0223] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)dimethyl,

[0224] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)dibenzyl,

[0225] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II), 1,4-diphenyl-1,3-butadiene,

[0226] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0227] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 2,4-hexadiene,

[0228](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(IV) 1,3-butadiene,

[0229](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

[0230](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) isoprene,

[0231](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II) 1,4-dibenzyl-1,3-butadiene,

[0232](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 2,4-hexadiene,

[0233](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II) 3-methyl-1,3-pentadiene,

[0234](tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl,(tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl,

[0235](tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,

[0236](tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl

[0237] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienylmethylphenylsilanetitanium (IV) dimethyl,

[0238] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienylmethylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

[0239]1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium(IV) dimethyl,

[0240] 1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium (II) 1,4-diphenyl-1,3-butadiene,

[0241] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

[0242] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) isoprene

[0243] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) dimethyl

[0244] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) dibenzyl

[0245] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) 1,3-butadiene,

[0246] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0247] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, and

[0248](tert-butylamido)(3-N-pyrrolidinylinden-1-yl)dimethylsilanetitanium (IV)dimethyl.

[0249] Other catalysts, especially catalysts containing other Group 4metals, will, of course, be apparent to those skilled in the art. Mosthighly preferred metal complexes for use herein are the following metalcomplexes:

[0250] (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,

[0251] (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II) 1,3-pentadiene,

[0252] (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,

[0253](cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II)1,3-pentadiene,cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II)1,4 diphenyl-1,3-butadiene,

[0254](cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II) 1,3-pentadiene,

[0255](cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,

[0256] (t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitaniumdimethyl,

[0257] (t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,3-pentadiene,

[0258] (t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,

[0259] (cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitaniumdimethyl,cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium (II)1,3-pentadiene,cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,4diphenyl-1,3-butadiene,

[0260](cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitaniumdimethyl,

[0261](cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,3-pentadiene,

[0262](cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

[0263](t-butylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitaniumdimethyl,

[0264](t-butylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,

[0265](t-butylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0266](cyclohexylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitaniumdimethyl,cyclohexylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,cyclohexylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0267](cyclododecylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitaniumdimethyl,

[0268](cyclododecylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,

[0269](cyclododecylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0270] (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0271](t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

[0272](t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0273](cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

[0274](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0275](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-penladiene,

[0276](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0277] (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0278] (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,3-pentadiene,

[0279] (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,

[0280](cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium((II)1,3-pentadiene,cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0281](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0282](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

[0283](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0284](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0285](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0286](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0287](cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0288](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0289](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0290](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0291](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0292](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0293](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium (II)1,4 diphenyl-1,3-butadiene,

[0294](cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0295](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0296](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0297](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0298] 1,2-ethanebis(inden-1-yl)zirconium dimethyl,

[0299] 1,2-ethanebis(inden-1-yl)zirconium(II) 1,3-pentadiene,1,2-ethanebis(inden-1-yl)zirconium(II) 1,4 diphenyl-1,3-butadiene,

[0300] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl,

[0301] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)1,3-pentadiene,

[0302] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,4diphenyl-1,3-butadiene,

[0303] dimethylsilanebis(inden-1-yl)zirconium dimethyl,

[0304] dimethylsilanebis(inden-1-yl)zirconium(II) 1,3-pentadiene,

[0305] dimethylsilanebis(inden-1-yl)zirconium(II) 1,4diphenyl-1,3-butadiene,

[0306] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl,

[0307] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)1,3-pentadiene, and

[0308] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,4diphenyl-1,3-butadiene.

[0309] The expanded anion cocatalysts of the invention may also be usedin combination with an oligomeric or polymeric alumoxane compound, atri(hydrocarbyl)aluminum compound, a di(hydrocarbyl)(hydrocarbyloxy)aluminum compound, adi(hydrocarbyl)(dihydrocarbyl-amido)aluminum compound, abis(dihydrocarbyl-amido) (hydrocarbyl)aluminum compound, adi(hydrocarbyl)amido(disilyl)aluminum compound, adi(hydrocarbyl)amido(hydrocarbyl)(silyl)aluminum compound, abis(dihydrocarbylamido)(silyl)aluminum compound, or a mixture of theforegoing compounds, having from 1 to 20 non-hydrogen atoms in eachhydrocarbyl, hydrocarbyloxy, or silyl group, if desired. These aluminumcompounds are usefully employed for their beneficial ability to scavengeimpurities such as oxygen, water, and aldehydes from the polymerizationmixture as well as to react with the hydroxyl group or quiescentreactive functionality of the compounds or the reactive derivativesthereof.

[0310] Preferred aluminum compounds include C₁₋₂₀ trialkyl aluminumcompounds, especially those wherein the alkyl groups are ethyl, propyl,isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl,dialkyl(aryloxy)aluminum compounds containing from 1-6 carbons in thealkyl group and from 6 to 18 carbons in the aryl group (especially(3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum), methylalumoxane,modified methalumoxane, especially isobutyl modified alumoxane, andtri(ethylaluminum)-, tris(pentafluorophenyl)borane-, ortris(pentafluorophenyl)aluminum-modified alumoxanes or supportedderivatives thereof. (The latter compositions are previously known,having been disclosed in WO99/15534. Additional species include mixturesof aluminum containing Lewis acids as disclosed in pending U.S. patentapplications Ser. Nos. 09/330,673 and 09/330,675. The molar ratio ofactivator to aluminum compound is preferably from 1:10,000 to 1000:1,more preferably from 1:5000 to 100:1, most preferably from 1:100 to100:1.

[0311] The cocatalysts of the present invention are capable ofactivating a wide variety of metal complexes. Moreover, the cocatalystscan be optimized in their ability to activate different metal complexesthrough combination of anions, Z*, having Lewis base sites of varyingbase strength, and Lewis acids, J*, having varying acidity. Thus, use ofderivatives of weakly basic anions such as dicyanamide, 1,2,4-triazolideand 4,5-dichloroimidazolide give expanded anion salts which are lessactive cocatalysts, all other variables being the same, than doderivatives of moderately basic anions, such as cyanide, azide,benzotriazolide, benzimidazolide and tetraimidazoylborate, which in turngive less active cocatalalysts than derivatives of even more basicanions, such as 4,4-dimethylimidazolinide, imidazolide,5,6-dimethylbenzimidazolide and 2-undecylimidazolide.

[0312] The equivalent ratio of catalyst/cocatalyst (calculated based onquantity of metal in the catalyst and anionic charges on the cocatalyst)employed preferably ranges from 1:10 to 10:1, more preferably from 1:5to 2:1, most preferably from 1:4 to 1:1. Mixtures of the activatingcocatalysts of the present invention may also be employed if desired.

[0313] Suitable addition polymerizable monomers include ethylenicallyunsaturated monomers, acetylenic compounds, conjugated or non-conjugateddienes, and polyenes. Preferred monomers include olefins, for examplesalpha-olefins having from 2 to 20,000, preferably from 2 to 20, morepreferably from 2 to 8 carbon atoms and combinations of two or more ofsuch alpha-olefins. Particularly suitable alpha-olefins include, forexample, ethylene, propylene, 1-butene, 1-pentene,4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, orcombinations thereof, as well as long chain vinyl terminated oligomericor polymeric reaction products formed during the polymerization, andC₁₀₋₃₀ α-olefins specifically added to the reaction mixture in order toproduce relatively long chain branches in the resulting polymers.Preferably, the alpha-olefins are ethylene, propene, 1-butene,4-methyl-pentene-1,1-hexene, 1-octene, and combinations of ethyleneand/or propene with one or more of such other alpha-olefins. Otherpreferred monomers include styrene, halo- or alkyl substituted styrenes,vinylbenzocyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidenenorbornene, and 1,7-octadiene. Mixtures of the above-mentioned monomersmay also be employed.

[0314] In general, the polymerization may be accomplished at conditionswell known in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions. Suspension, solution, slurry, gas phase orhigh pressure, whether employed in batch or continuous form or otherprocess conditions, may be employed if desired. Examples of such wellknown polymerization processes are depicted in WO 88/02009, U.S. Pat.Nos. 5,084,534, 5,405,922, 4,588,790, 5,032,652, 4,543,399, 4,564,647,4,522,987, and elsewhere. Preferred polymerization temperatures are from0-250° C. Preferred polymerization pressures are from atmospheric to3000 atmospheres.

[0315] Suitable processing conditions include solution polymerization,more preferably continuous solution polymerization processes, conductedin the presence of an aliphatic or alicyclic liquid diluent, preferablyusing the unsupported, quiescent reactive functionality containingcompounds. By the term “continuous polymerization” is meant that atleast the products of the polymerization are continuously removed fromthe reaction mixture, such as for example by devolatilization of aportion of the reaction mixture. Preferably one or more reactants arealso continuously added to the polymerization mixture during thepolymerization. Examples of suitable aliphatic or alicyclic liquiddiluents include straight and branched-chain C₄₋₁₂ hydrocarbons andmixtures thereof; alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; and perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and the like. Suitable diluents also include aromatichydrocarbons (particularly for use with aromatic α-olefins such asstyrene or ring alkyl-substituted styrenes) including toluene,ethylbenzene or xylene, as well as liquid olefins (which may act asmonomers or comonomers) including ethylene, propylene, butadiene,cyclopentene, 1-hexene, 3-methyl-1pentene, 4-methyl-1-pentene,1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene,allylbenzene, vinyltoluene (including all isomers alone or inadmixture), and the like. Mixtures of the foregoing are also suitable.The foregoing diluents may also be advantageously employed during thesynthesis of the metal complexes and catalyst activators of the presentinvention.

[0316] In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 0.1:1, morepreferably from 10⁻¹²:1 to 10⁻⁵:1.

[0317] The catalyst composition of the invention may also be utilized incombination with at least one additional homogeneous or heterogeneouspolymerization catalyst in separate reactors connected in series or inparallel to prepare polymer blends having desirable properties. Anexample of such a process is disclosed in WO 94/00500.

[0318] Molecular weight control agents can be used in combination withthe present cocatalysts. Examples of such molecular weight controlagents include hydrogen, trialkyl aluminum compounds or other knownchain transfer agents. A particular benefit of the use of the presentcocatalysts is the ability (depending on reaction conditions) to producenarrow molecular weight distribution α-olefin homopolymers andcopolymers in greatly improved catalyst efficiencies. Preferred polymershave Mw/Mn of less than 2.5, more preferably less than 2.3. Such narrowmolecular weight distribution polymer products are highly desirable dueto improved tensile strength properties.

[0319] The catalyst composition of the present invention can also beemployed to advantage in the gas phase polymerization andcopolymerization of olefins. Gas phase processes for the polymerizationof olefins, especially the homopolymerization and copolymerization ofethylene and propylene, and the copolymerization of ethylene with higheralpha olefins such as, for example, 1-butene, 1-hexene,4-methyl-1-pentene are well known in the art. Such processes are usedcommercially on a large scale for the manufacture of high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE) and polypropylene.

[0320] The gas phase process employed can be, for example, of the typewhich employs a mechanically stirred bed or a gas fluidized bed as thepolymerization reaction zone. Preferred is the process wherein thepolymerization reaction is carried out in a vertical cylindricalpolymerization reactor containing a fluidized bed of polymer particlessupported above a perforated plate, the fluidisation grid, by a flow offluidisation gas.

[0321] The gas employed to fluidize the bed comprises the monomer ormonomers to be polymerized, and also serves as a heat exchange medium toremove the heat of reaction from the bed. The hot gases emerge from thetop of the reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a wider diameter than the fluidized bedand wherein fine particles entrained in the gas stream have anopportunity to gravitate back into the bed. It can also be advantageousto use a cyclone to remove ultra-fine particles from the hot gas stream.The gas is then normally recycled to the bed by means of a blower orcompressor and one or more heat exchangers to strip the gas of the heatof polymerization.

[0322] A preferred method of cooling of the bed, in addition to thecooling provided by the cooled recycle gas, is to feed a volatile liquidto the bed to provide an evaporative cooling effect. The volatile liquidemployed in this case can be, for example, a volatile inert liquid, forexample, a saturated hydrocarbon having about 3 to about 8, preferably 4to 6, carbon atoms. In the case that the monomer or comonomer itself isa volatile liquid, or can be condensed to provide such a liquid this canbe suitably be fed to the bed to provide an evaporative cooling effect.Examples of olefin monomers which can be employed in this manner areolefins containing from about 3 to about eight, preferably from 3 to sixcarbon atoms. The volatile liquid evaporates in the hot fluidized bed toform gas which mixes with the fluidizing gas. If the volatile liquid isa monomer or comonomer, it will undergo some polymerization in the bed.The evaporated liquid then emerges from the reactor as part of the hotrecycle gas, and enters the compression/heat exchange part of therecycle loop. The recycle gas is cooled in the heat exchanger and, ifthe temperature to which the gas is cooled is below the dew point,liquid will precipitate from the gas. This liquid is desirably recycledcontinuously to the fluidized bed. It is possible to recycle theprecipitated liquid to the bed as liquid droplets carried in the recyclegas stream, as described, for example, in EP-A-89691, U.S. Pat. No.4,543,399, WO 94/25495 and U.S. Pat. No. 5,352,749. A particularlypreferred method of recycling the liquid to the bed is to separate theliquid from the recycle gas stream and to reinject this liquid directlyinto the bed, preferably using a method which generates fine droplets ofthe liquid within the bed. This type of process is described in WO94/28032.

[0323] The polymerization reaction occurring in the gas fluidized bed iscatalyzed by the continuous or semi-continuous addition of catalyst.Such catalyst can be supported on an inorganic or organic supportmaterial if desired. The catalyst can also be subjected to aprepolymerization step, for example, by polymerizing a small quantity ofolefin monomer in a liquid inert diluent, to provide a catalystcomposite comprising catalyst particles embedded in olefin polymerparticles.

[0324] The polymer is produced directly in the fluidized bed bycatalyzed (co)polymerization of the monomer(s) on the fluidizedparticles of catalyst, supported catalyst or prepolymer within the bed.Start-up of the polymerization reaction is achieved using a bed ofpreformed polymer particles, which, preferably, is similar to the targetpolyolefin, and conditioning the bed by drying with inert gas ornitrogen prior to introducing the catalyst, the monomer(s) and any othergases which it is desired to have in the recycle gas stream, such as adiluent gas, hydrogen chain transfer agent, or an inert condensable gaswhen operating in gas phase condensing mode. The produced polymer isdischarged continuously or discontinuously from the fluidized bed asdesired, optionally exposed to a catalyst kill and optionallypelletized.

[0325] Slurry polymerization conditions and supported catalystpreparation techniques for use therein are well known from the publishedliterature. Generally such catalysts are prepared by the same techniquesas are employed for making supported catalysts used in gas phasepolymerizations. Slurry polymerization conditions generally encompasspolymerization of a C₂₋₂₀ olefin, diolefin, cycloolefin, or mixturethereof in an aliphatic solvent at a temperature below that at which thepolymer is readily soluble in the presence of a supported catalyst.Slurry phase processes particularly suited for the polymerization ofC₂₋₆ olefins, especially the homopolymerization and copolymerization ofethylene and propylene, and the copolymerization of ethylene with C₃₋₈α-olefins such as, for example, 1-butene, 1-hexene, 4-methyl-1-penteneand 1-octene are well known in the art. Such processes are usedcommercially on a large scale for the manufacture of high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE) and polypropylene, especially isotacticpolypropylene.

EXAMPLES

[0326] It is understood that the present invention is operable in theabsence of any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of about20-25° C., and “mixed alkanes” refers to a mixture of mostly C₆-C₁₂alkanes available commercially under the trademark Isopar ETM from ExxonChemicals Inc.

[0327] All manipulation of air sensitive materials was performed in anargon filled, vacuum atmospheres, glove box or on a high vacuum lineusing standard Shlenk techniques. Toluene was purified by passagethrough columns packed with activated alumina (Kaiser A-2) and supportedcopper (Engelhard, Cu-0224 S). Hexanes were purified by distillationfrom sodium benzophenone ketyl. Tris(pentafluorophenyl)borane waspurchased from Boulder Scientific. Potassium azide was purchased fromAtomergic Chemetals Corp., and used as received. Dioctadecylmethylamineis a bis(hydrogenated tallow) alkylamine of approximate formulation(C₁₈H₃₅)₂CH₃N, available commercially under the tradename Armeen™ M2HTfrom Akzo Nobel, Inc., and was used as received.

Example 1

[0328] A) Synthesis of 2-(4-hydroxyphenyl)imidazole—HOC₆H₄C₃H₃N₂

[0329] A flask was charged with 4-hydroxybenzaldehyde (30.0 g, 0.246mol) and conc. ammonium hydroxide (36 mL). The solution was cooled to 0°C. and glyoxal (45 mL, 0.392 mol) was added dropwise via syringe over 30minutes. A yellow precipitate formed and the slurry was stirred andallowed to warm to 25° C. for two hours. The product was collected on afrit, washed with cold water, and dried under reduced pressure to give ayellow powder (29.4 g, 75 percent yield). The solid was recrystallizedfrom dimethylformamide (DMF) to give a tan powder.

[0330]¹H NMR (DMSO) δ 12.23 (br s, 1 H, NH), 9.72 (br s, 1 H, OH), 7.74(d, J=8.6 Hz, 2H, Ph), 7.04 (s, 2H, imidazole CH═CH), 6.81 (d, J=8.6 Hz,2H, Ph).

[0331]¹³C NMR (DMSO) δ 157.46 (Ph COH), 146.06 (Ph CCN₂HCH₂), 132.17(CN₂HC—₂H₂),126.37 (Ph CH), 122.26 (CN₂HC ₂H₂), 115.41 (Ph CH). MS (M+H⁺161.0).

[0332] B) Synthesis of2-(4-trimethylsiloxyphenyl)imidazole—TMSOC₆H₄C₃H₃N₂

[0333] A flask was charged with the 2-(4-hydroxyphenyl)imidazole (1.00g, 6.24 mmol) and 25 mL of CH₂Cl₂. To the slurry was addedtrimethylsilylchloride and triethylamine via syringe. The mixtureclarified to give an amber soluiton. After stirring for 3 hours at 25°C., the volatiles were removed and the residue triturated once withhexanes and then dissolved in toluene. Filtration through diatomaceousearth filter aid and recystallizaiton from toluene yielded 0.914 g (63percent yield) of the desired product as a tan solid.

[0334]¹H NMR (CH₂Cl₂) δ 12.63 (s, 1H, NH), 7.80 (d, J=8.5 Hz, 2H, Ph),7.11 (s, 2H, imidazole CH═CH), 6.81 (d, J=8.5 Hz, 2H, Ph), 0.26 (s, 9H,SiMe ₃).

[0335]¹³C NMR (CH₂Cl₂) δ 156.32 (Ph COSiMe₃), 147.74 (Ph CCN₂HCH₂),127.62 (Ph CH), 124.70 (CN₂HC₂H₂), 123.28 (CN₂HC ₂H₂), 120.89 (Ph CH),0.39 (SiMe ₃).

[0336] MS (M⁺ 232.1).

[0337] C) Preparation of [H(C₁₈H₃₅)₂(CH₃)N]⁺{(HOC₆H₄C₃H₂N₂)[B(C₆F₅)₃]₂}⁻

[0338] A vial was charged with 2-(4-hydroxyphenyl)imidazole (20.2 mg,0.126 mmol), tris(pentafluorophenyl)borane (128.7 mg, 0.251 mmol),di(octadecyl)methylamine (66.8 mg, 0.128 mmol), and 2.0 mL ofd₈-toluene. The mixture was stirred for 10 minutes until all of thesolids dissolved and then analyzed to determine the product's identity.

[0339]¹H NMR (d₈-toluene) δ 6.82 (br s, 1H, OH), 6.47 (d, J=8.8 Hz, 2H,Ph), 6.85 (d, J=8.6 Hz, 2H, Ph), 5.85 (t, J=2.3 Hz, 2H, imidazoleCH═CH), 4.07 (v br s, 1H, NH), 2.24 (m, 2H, HNCH ₂), 2.05 (partiallyobsured m, 2H, HNCH ₂), 1.91 (d, J=5.1 Hz, 3H, NMe), 1.4-1.0 (amineCH₂), 0.93 (t, J=6.7 Hz, 6H, N(CH₂)_(n)CH ₃).

[0340]¹⁹F NMR (d₈-toluene) δ o-CF [−127.29 (“d”, 1F), −132.72 (“d”, 1F),−133.45 & −133.75 (br m & “d”), 10F], p-CF [−156.66 (t, J=19.8 Hz, 1F),−159.09 (t, J=19.3 Hz, 2F), −160.79 (t, J=22.0 Hz, 3F)], m-CF [−162.96(“br t”, J=22.9 Hz, 1F), −163.64 (“br t”, J=21.4 Hz, 1F), −165.78 &−166.12 (m & br m, 10F)].

[0341] MS cation [(M⁺ 537.5) fragments 536.5, 509.5, 508.5 (base),480.5)], anion {(M⁻ 1182.6) fragments 872.7, 670.6 [base, (M—B(C₆F₅)₃⁻)], 632.6}.

Example 2

[0342] Large Scale Preparation of[H(C₁₈H₃₅)₂(CH₃)N]⁺{(HOC₆H₄C₃H₂N₂)[B(C₆F₅)₃]₂}⁻

[0343] A 250 mL flask was charged with 2-(4-hydroxyphenyl)imidazole(03.16 g, 1.97 mmol), tris(pentafluorophenyl)borane (2.02 g, 3.95 mmol),dioctadecylmethylamine (1.02 g, 1.96 mmol), and 100 mL of toluene. Themixture was stirred for 1 hour and then filtered through a frit. Thevolatiles were removed under reduced pressure to give a viscous, brownoil (3.10 g, 92.4 percent yield).

Example 3

[0344] Preparation of [H(C₆H₅)(CH₃)₂N]⁺{(Me₃SiOC₆H₄C₃H₂N₂)[B(C₆F₅)₃]₂}⁻

[0345] A vial was charged with 2-(4-trimethylsiloxyphenyl)imidazole(20.4 mg, 0.088 mmol), tris(pentafluorophenyl)borane (90.0 mg, 0.176mmol), ), dioctadecylmethylamine (47.0 mg, 0.090 mmol), and 2.0 mL ofd₈-toluene. The cloudy mixture was stirred for 10 minutes untildissolved. The solution was analyzed for product identity.

[0346]¹H NMR (d₈-toluene) δ 7.21 (br s, 2H, imidazole CH═CH), 6.65 (brd, J=7.8 Hz, 2H, Ph), 6.39 (d, J=8.8 Hz, 2H, Ph), 3.95 (v br s, 1H, NH),2.04 (br m, 4H, HNCH ₂), 1.77 (s, 3H, NMe), 1.4-1.0 (amine CH₂), 0.93(t, J=6.8 Hz, N(CH₂)_(n)CH ₃ overlaps with some amine resonances), 0.12(s, 9H, SiMe ₃).

[0347]¹⁹F NMR (d₈-toluene) δ o-CF [−125.71 (br s, 2F), −132.5 & −132.43(v br m & br s), 10F], p-CF [−157.85 (t, J=21.4 Hz, 2F), −160.28 (br“t”, 4F)], m-CF [−163.78 (“br t”, 2F), −164.37 (br s, 2F), −166.50 (v brs, 8F)].

[0348] MS cation [(M⁺ 537.6) fragments 536.5, 509.6, 508.6 (base),480.6)], anion {(M⁻ 1254.8) fragments 742.6 [base, (M—B(C₆F₅)3⁻)]}.

Example 4

[0349] Preparation of[H(C₁₈H₃₅)₂(CH₃)N]⁺{(Me₃SiOC₆H₄C₃H₂N₂)[Al(C₆F₅)₃]₂}⁻

[0350] A vial was charged with 2-(4-trimethylsiloxyphenyl)imidazole(20.5 mg, 0.088 mmol), tris(pentafluorophenyl)aluminane.½(toluene)(103.1 mg, 0.180 mmol), di(octadecyl)methylamine (46.0 mg, 0.088 mmol),and 2.0 mL of d₈-toluene. The mixture was stirred for 15 minutes untilall of the solids dissolved and then analyzed.

[0351]¹H NMR (d₈-toluene) δ 7.40 (s, 2H, imidazole CH═CH), 7.31 (d,J=8.5 Hz, 2H, Ph), 6.36 (d, J=8.6 Hz, 2H, Ph), 4.35 (v br s, 1H, NH),2.01 (br m, 4H, HNCH ₂), 1.73 (s, 3H, NMe), 1.4-1.0 (amine CH₂), 0.93(t, J=6.6 Hz, N(CH₂)_(n)CH ₃ overlaps with some amine resonances), 0.12(s, 9H, SiMe ₃).

[0352]¹⁹F NMR (d₈-toluene) δ −121.79 (dd, J=27.4 & 18.3, 2F, o-CF),−155.02 (t, J=19.8 Hz, 1F, p-CF), −162.73 (m, 2F, m-CF).

[0353] MS cation [(M⁺ 537.8) fragments 536.8, 509.8, 508.8, (base),480.7], anion [M⁻ 1286.9 (base)].

Example 5

[0354] Preparation of[H(C₁₈H₃₅)₂(CH₃)N]⁺{(Et₂AlOC₆H₄C₃H₂N₂)[B(C₆F₅)₃]₂}⁻(di(octadecyl)methylammonium2-(4-diethylaluminoxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane])

[0355] Under an argon atmosphere, a toluene solution ofdi(octadecyl)methyl-ammonium 2-(4-hydroxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane]([H(C₁₈H₅)₂(CH₃)N]⁺{(HOC₆H₄C₃H₂N₂)[B(C₆F₅)₃]₂}, 825 μl, 0.040M, 33.0μmol) and a toluene solution of triethyl aluminum (363 μl, 0.10M, 36.3μmol) were added to a vial and mixed for 30 seconds. Formation of thedesired product can be identified by nuclear magnetic resonancespectroscopy.

Example 6a and 6b

[0356] Preparation of Supported Catalyst SystemDi(octadecyl)methylammonium 2-(4-hydroxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane] on TEA/silica

[0357] Under an argon atmosphere, a toluene solution ofdi(octadecyl)methyl ammonium 2-(4-hydroxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane]([H(C₁₈H₃₅)₂(CH₃)N]⁺{(HOC₆H₄C₃H₂N₂)[B(C₆F₅)₃]₂}⁻, 825 μl, 0.040M, 33.0μmol) was diluted to 1500 μl with toluene and added to 1.00 g oftriethylaluminum (TEA)-treated silica (Grace-Davison 948 silica,available from Grace-Davison Company, heated at 250° C. for 4 h, treatedwith 1.5 mmol TEA/g, washed with toluene and hexanes and dried underreduced pressure). The mixture was shaken by hand to break-up clumps andthen mechanically agitated for 5 minutes. The volatiles were thenremoved under reduced pressure. A toluene solution of(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silane titanium1,3-pentadiene (1500 μl, 0.020M, 30.0 μmol) was added to the TEA-treatedsilica. The mixture was shaken by hand to break-up clumps and thenmechanically agitated for 5 minutes. The volatiles were then removedunder reduced pressure to give an olive green solid (0.988 g).

Example 7

[0358] Preparation of Supported Catalyst System

[0359] Di(octadecyl)methylammonium2-(4-diethylaluminoxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane] on TEA/silica

[0360] Under an argon atmosphere, a toluene solution ofdi(octadecyl)methyl-ammonium 2-(4-hydroxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane] (825 μl, 0.040M, 33.0 μmol) and atoluene solution of triethyl aluminum (363 μl, 0.10M, 36.3 μmol) wereadded to a vial and mixed for 30 seconds. This solution was then addedto 1.00 g of TEA-treated silica (Grace-Davison 948, heated at 250° C.for 4 h, treated with 1.5 mmol TEA/g, washed with toluene and hexanesand dried under reduced pressure). The mixture was shaken by hand tobreak-up clumps and then mechanically agitated for 5 minutes. Thevolatiles were then removed under reduced pressure. A toluene solutionof (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium1,3-pentadiene (1500 μl, 0.020M, 30.0 μmol) was added to the silica. Themixture was shaken by hand to break-up clumps and then mechanicallyagitated for 5 minutes. The volatiles were then removed under reducedpressure to give the desired supported catalyst product as an olivegreen solid (1.00 g).

Example 8

[0361] Preparation of Supported Catalyst System

[0362] Di(octadecyl)methylammonium 2-(4-hydroxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane] w/(EBI)Zr(DPB) on TEA/silica

[0363] Under an argon atmosphere, a toluene solution ofdi(octadecyl)methyl ammonium 2-(4-hydroxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane]([H(C₁₈H₃₅)₂(CH₃)N]⁺{(HOC₆H₄C₃H₂N₂)[B(C₆F₅)₃]₂}⁻, 825 μl, 0.040M, 33.0μmol) was diluted to 1500 μl with toluene and added to 1.00 g oftriethylaluminum (TEA)-treated silica (Grace-Davison 948 silica,available from Grace-Davison Company heated at 250° C. for 4 h, treatedwith 1.5 mmol TEA/g, washed with toluene and hexanes and dried underreduced pressure). The mixture was shaken by hand to break-up clumps andthen mechanically agitated for 5 minutes. The volatiles were thenremoved under reduced pressure. A toluene solutionrac-ethylenebis(indenyl)zirconium(1,4-diphenylbutadene) (1500 μl,0.020M, 30.0 μmol) was added to the TEA-treated silica. The mixture wasshaken by hand to break-up clumps and then mechanically agitated for 5minutes. The volatiles were then removed under reduced pressure to givea purple-gray solid (1.061 g).

Example 9

[0364] Preparation of Supported Catalyst System

[0365] Di(octadecyl)methylammonium2-(4-diethylaluminoxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane] w/(EBI)Zr(DPB) on TEA/silica

[0366] Under an argon atmosphere, a toluene solution ofdi(octadecyl)methyl-ammonium 2-(4-hydroxyphenyl)imidazolatebis[tris(pentafluorophenyl)borane] (825 μl, 0.040M, 33.0 μmol) and atoluene solution of triethyl aluminum (363 μl, 0.10M, 36.3 μmol) wereadded to a vial and mixed for 30 seconds. This solution was then addedto 1.00 g of TEA-treated silica (Grace-Davison 948, heated at 250° C.for 4 h, treated with 1.5 mmol TEA/g, washed with toluene and hexanesand dried under reduced pressure). The mixture was shaken by hand tobreak-up clumps and then mechanically agitated for 5 minutes. Thevolatiles were then removed under reduced pressure. A toluene solutionrac-ethylenebis(indenyl)zirconium(1,4-diphenylbutadene) (1500 μl,0.020M, 30.0 μmol) was added to the silica. The mixture was shaken byhand to break-up clumps and then mechanically agitated for 5 minutes.The volatiles were then removed under reduced pressure to give thedesired supported catalysts product as a purple-gray solid (1.065 g).

[0367] Gas Phase Polymerizations

[0368] A 2.5-L stirred, fixed bed autoclave was charged with 200 g dryNaCl containing 0.1 g of KH as a scavenger. Stirring was begun at 300rpm. The reactor was pressurized to 0.8 MPa ethylene and heated to 70°C. 1-hexene (7000 ppm) was introduced to the reactor followed by theaddition of hydrogen (when used). In a separate vessel, 0.05 g ofcatalyst was mixed with an additional 0.1 g KH scavenger. The combinedcatalyst and scavenger were subsequently injected into the reactor.Ethylene pressure was maintained on demand while hexene and hydrogen(where used) were fed to the reactor to maintain their respectiveconcentrations. The temperature of the reactor was regulated by acirculating water bath. After 90 minutes the reactor was depressurized,and the salt and polymer were removed. The polymer was washed withcopious quantities of distilled water to remove the salt, dried at 60°C., and then stabilized by addition of a hindered phenol antioxidant(Irganox™ 1010 from Ciba Geigy Corporation) and 133 mg of a phosphorusstabilizer. Activity values were calculated based on ethylene uptake.Results are shown in Table 1. TABLE 1 Co- H₂ Activity Run Catalystcatalyst (ppm) (g/ghb)³ Density I₂ Mw 1 T¹ Ex 6 2000 18.0 0.912 0.296139,000 2 E² Ex 8 0 59.9 0.922 <0.300   210,000 3 ″ ″ 2000 36.7 0.921.017  92,500 4 T¹ Ex 7 2000 25.3 0.914 0.92 117,000 5 E² Ex 9 0 75.70.924 <1.04    191,000 6 ″ ″ 2000 47.8 0.927 3.22 110,000 7 ″ ″ 0 64.30.924 <1.233 193,000

What is claimed is:
 1. A compound corresponding to the formula:(A*^(+a))_(b)(Z*J*_(j))^(−c) _(d), wherein: A* is a cation of from 1 to80, preferably 1 to 60 atoms, not counting hydrogen atoms, said A*having a charge +a, Z* is an anion group of from 1 to 50, preferably 1to 30 atoms, not counting hydrogen atoms, further containing two or moreLewis base sites; J* independently each occurrence is a Lewis acid offrom 1 to 80, preferably 1 to 60 atoms, not counting hydrogen atoms,coordinated to at least one Lewis base site of Z*, and optionally two ormore such J* groups may be joined together in a moiety having multipleLewis acidic functionality, j is a number from 2 to 12 and a, b, c, andd are integers from 1 to 3, with the proviso that a×b is equal to c×d,and provided further that one or more of A*, Z* or J* comprises ahydroxyl group or a polar group containing quiescent reactivefunctionality.
 2. A compound according to claim 1 wherein A*^(+a) isselected from the group consisting of ammonium, sulfonium, phosphonium,oxonium, carbonium, silylium, ferrocenium, Ag⁺, and Pb⁺² cations.
 3. Acompound according to claim 1 wherein Z* is selected from the groupconsisting of trialkylsiloxy-, trialkylsiloxyalkyl-,trialkylsiloxyaryl-, and dialkylaluminoxyaryl-substituted derivatives ofimidazolide, 2-(C₁₋₃₀hydrocarbyl)imidazolide, 4,5-dihaloimidazolide,4,5-di(C₁₋₃₀hydrocarbyl)imidazolide, 4,5-benzylimidazolide,2-(C₁₋₃₀hydrocarbyl)-4,5-benzimidazolide, 1,3,4-triazolide,2-(C₁₋₃₀hydrocarbyl-1,3,4-triazolide, 1,2,3-triazolide,4,5-benz-1,2,3-triazolide, imidazolinide,2-(C₁₋₃₀hydrocarbyl)imidazolinide, 4,5-dihaloimidazolinide, and5,6-dimethylbenzimidazolide.
 4. A compound according to claim 1 which isan ammonium, phosphonium, sulfonium, oxonium, carbonium, silylium, lead(II), silver or ferrocenium salt of hydroxylphenyl-,trimethylsiloxyphenyl-, and dialkylaluminoxyphenyl-substitutedderivatives of: bis(tris(penta-fluorophenyl)borane)-imidazolide,bis(tris(pentafluorophenyl)borane)-2-undecyl-imidazolide,bis(tris(pentafluorophenyl)borane)imidazolinide,bis(tris(pentafluorophenyl)-borane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-benzimidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)borane)1,3,4-triazolide,bis(tris(pentafluorophenyl)borane)-2-undecyl-1,3,4-triazolide,bis(tris(pentafluorophenyl)alumane)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)alumane)imidazolinide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-4,5-benzimidazolide,bis(tris(pentafluoro-phenyl)alumane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-1,3,4-triazolide, orbis(tris(pentafluorophenyl)alumane)-2-undecyl-1,3,4-triazolide.
 5. Aammonium salt compound according to claim 1 wherein the ammonium cationis a trimethylammonium-, triethylammonium-, tripropylammonium-,tri(n-butyl)ammonium-, methyldi(octadecyl)ammonium-,methyldi(tetradecyl)ammonium-, methyl(tetradecyl)(octadecyl)ammonium-,N,N-dimethylanilinium-, N,N-diethylanilinium-,N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-,N,N-di(tetradecyl)-2,4,6-trimethylanilinium)-,N,N-di(octadecyl)lanilinium-,N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, ormethyldicyclohexylammonium-cation.
 6. A compound according to claim 1corresponding to the formula:

wherein: A*⁺ is a monovalent cation as previously defined in claim 1,R⁴, independently each occurrence, is hydrogen or a hydroxyhydrocarbyl,halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, orsilyl group, (including mono-, di- and tri(hydrocarbyl)silyl) group ofup to 30 atoms not counting hydrogen, preferably C₁₋₂₀ alkyl group, or aquiescent reactive group, with the proviso that at least one R⁴ groupcontains a hydroxyhydrocarbyl group or a quiescent reactive group, andJ*′ is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).7. A compound according to claim 1 that is a trihydrocarbylammonium-saltof: bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-hydroxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-hydroxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)imidazolinide,bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-1,3,4-triazolide,bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-benziimidazolide;bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-trimethylsiloxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-trimethylsiloxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)imidazolinide,bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-1,3,4-triazolide,bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-benziimidazolide;bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-diethylaluminoxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-diethylaluminoxyphenyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imidazolinide,bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-1,3,4-triazolide,bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-benziimidazolide;bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-hydroxyphenyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-hydroxyphenyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-1,3,4-triazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-benziimidazolide;bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-trimethylsiloxyphenyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-trimethylsiloxyphenyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-1,3,4-triazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-benziimidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-diethylaluminoxyphenyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-diethylaluminoxyphenyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-1,3,4-triazolide,orbis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-benziimidazolide.8. A catalyst composition for polymerization of addition polymerizablemonomers comprising, in combination, 1) a Group 3-10 or Lanthanide metalcomplex, preferably a Group 4 metal complex, 2) a compound according toany one of claims 1-7, or the reaction product of 1 and 2), andoptionally 3) a solid, particulated support.
 9. A catalyst compositionfor polymerization of a-olefins comprising, in combination, 1) a Group3-10 or Lanthanide metal complex, preferably a Group 4 metal complex and2) a compound according to any one of claims 1-7.
 10. A catalystcomponent for use in formation of heterogeneous catalyst compositions,comprising, in combination, a compound according to any one of claims1-7 and a solid, particulated support.
 11. The component of claim 10wherein the support is silica.
 12. The component of claim 11 wherein thesilica is dried and reacted with a trialkylaluminum compound to removereactive functionality thereon before contacting with the metal complexor compound.
 13. A polymerization process comprising contacting one ormore α-olefins under polymerization conditions with a catalystcomposition or component according to claim
 8. 14. A polymerizationprocess according to claim 13 that is a slurry polymerization.
 15. Apolymerization process according to claim 13 that is a gas phasepolymerization.